The conductive nano-Al/polyaniline composites were prepared by the milling method in the solid state. Here, aluminum nanostructures were prepared in two different mechanical methods, wire drawing and wire milling in the presence of lubricant oil. The effects of the preparation methods on the structures and morphologies of aluminum nanostructures were investigated by XRD and FESEM. The results show that the shape and size of aluminum nanoparticles in the preparation by the wire drawing method are significantly different than the wire milling method. The aluminum nanostructures were prepared by milling method have flake-like nanosheets while the wire drawing method leads to the formation of spherical ultrafine nanoparticles, which particles size are in the range of 30–60 nm. Then, polyaniline was produced using a solid-state polymerization process by the chemical reaction between aniline hydrochloride and potassium peroxydisulfate. Finally, nano-Al/polyaniline composites were prepared by mechanical milling at room temperature. The quantitative analysis was carried out with the materials analysis using diffraction (MAUD) method and weight fraction for aluminum and PANI were calculated 6.66% and 93.34%, respectively. Electrical conductivity measurements show the conductivity (1.2 × 10−2 S cm−1 at 25 °C) for polyaniline emeraldine salt and (1.02 × 10−3 S cm−1 at 25 °C) in nanocomposite respectively. The results show that by adding aluminum nanoparticles to the polymer the conductivity of nanocomposite (Al/PANI-ES) is lower than that for pure (PANI-ES). Thermogravimetry and differential thermal analysis curves show pure (PANI-ES) and nanocomposite (Al/PANI-ES) have a similar thermal degradation process. The total weight loss in TG curve of pure PANI-ES, in the temperature range 45–800 °C is 46.28% but, total weight loss observed in nanocomposite is 38.67%. Therefore, nanocomposite has higher thermal stability than that of the pure PANI-ES.
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